CN108998799B - Corrosion inhibitor for oil refining device and preparation method and application thereof - Google Patents
Corrosion inhibitor for oil refining device and preparation method and application thereof Download PDFInfo
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- CN108998799B CN108998799B CN201810820288.5A CN201810820288A CN108998799B CN 108998799 B CN108998799 B CN 108998799B CN 201810820288 A CN201810820288 A CN 201810820288A CN 108998799 B CN108998799 B CN 108998799B
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- 230000007797 corrosion Effects 0.000 title claims abstract description 105
- 238000005260 corrosion Methods 0.000 title claims abstract description 105
- 239000003112 inhibitor Substances 0.000 title claims abstract description 70
- 238000007670 refining Methods 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 55
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000010438 heat treatment Methods 0.000 claims abstract description 16
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 12
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 229960000583 acetic acid Drugs 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 239000012362 glacial acetic acid Substances 0.000 claims abstract description 8
- WBHHMMIMDMUBKC-XLNAKTSKSA-N ricinelaidic acid Chemical compound CCCCCC[C@@H](O)C\C=C\CCCCCCCC(O)=O WBHHMMIMDMUBKC-XLNAKTSKSA-N 0.000 claims abstract description 8
- 229960003656 ricinoleic acid Drugs 0.000 claims abstract description 8
- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003085 diluting agent Substances 0.000 claims abstract description 7
- 150000001412 amines Chemical class 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 8
- RUFPHBVGCFYCNW-UHFFFAOYSA-N 1-naphthylamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1 RUFPHBVGCFYCNW-UHFFFAOYSA-N 0.000 claims description 6
- MKARNSWMMBGSHX-UHFFFAOYSA-N 3,5-dimethylaniline Chemical compound CC1=CC(C)=CC(N)=C1 MKARNSWMMBGSHX-UHFFFAOYSA-N 0.000 claims description 6
- UFFBMTHBGFGIHF-UHFFFAOYSA-N 2,6-dimethylaniline Chemical compound CC1=CC=CC(C)=C1N UFFBMTHBGFGIHF-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- JDMFXJULNGEPOI-UHFFFAOYSA-N 2,6-dichloroaniline Chemical compound NC1=C(Cl)C=CC=C1Cl JDMFXJULNGEPOI-UHFFFAOYSA-N 0.000 claims description 3
- YQLZOAVZWJBZSY-UHFFFAOYSA-N decane-1,10-diamine Chemical compound NCCCCCCCCCCN YQLZOAVZWJBZSY-UHFFFAOYSA-N 0.000 claims description 3
- 239000002283 diesel fuel Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- HKUFIYBZNQSHQS-UHFFFAOYSA-N n-octadecyloctadecan-1-amine Chemical compound CCCCCCCCCCCCCCCCCCNCCCCCCCCCCCCCCCCCC HKUFIYBZNQSHQS-UHFFFAOYSA-N 0.000 claims description 3
- WRDGNXCXTDDYBZ-UHFFFAOYSA-N 2,3,4-trifluoroaniline Chemical compound NC1=CC=C(F)C(F)=C1F WRDGNXCXTDDYBZ-UHFFFAOYSA-N 0.000 claims description 2
- BRPSAOUFIJSKOT-UHFFFAOYSA-N 2,3-dichloroaniline Chemical compound NC1=CC=CC(Cl)=C1Cl BRPSAOUFIJSKOT-UHFFFAOYSA-N 0.000 claims description 2
- GUMCAKKKNKYFEB-UHFFFAOYSA-N 2,4,5-trichloroaniline Chemical compound NC1=CC(Cl)=C(Cl)C=C1Cl GUMCAKKKNKYFEB-UHFFFAOYSA-N 0.000 claims description 2
- KWVPRPSXBZNOHS-UHFFFAOYSA-N 2,4,6-Trimethylaniline Chemical compound CC1=CC(C)=C(N)C(C)=C1 KWVPRPSXBZNOHS-UHFFFAOYSA-N 0.000 claims description 2
- NATVSFWWYVJTAZ-UHFFFAOYSA-N 2,4,6-trichloroaniline Chemical compound NC1=C(Cl)C=C(Cl)C=C1Cl NATVSFWWYVJTAZ-UHFFFAOYSA-N 0.000 claims description 2
- DYSRXWYRUJCNFI-UHFFFAOYSA-N 2,4-dibromoaniline Chemical compound NC1=CC=C(Br)C=C1Br DYSRXWYRUJCNFI-UHFFFAOYSA-N 0.000 claims description 2
- KQCMTOWTPBNWDB-UHFFFAOYSA-N 2,4-dichloroaniline Chemical compound NC1=CC=C(Cl)C=C1Cl KQCMTOWTPBNWDB-UHFFFAOYSA-N 0.000 claims description 2
- CEPCPXLLFXPZGW-UHFFFAOYSA-N 2,4-difluoroaniline Chemical compound NC1=CC=C(F)C=C1F CEPCPXLLFXPZGW-UHFFFAOYSA-N 0.000 claims description 2
- SDYWXFYBZPNOFX-UHFFFAOYSA-N 3,4-dichloroaniline Chemical compound NC1=CC=C(Cl)C(Cl)=C1 SDYWXFYBZPNOFX-UHFFFAOYSA-N 0.000 claims description 2
- AXNUZKSSQHTNPZ-UHFFFAOYSA-N 3,4-difluoroaniline Chemical compound NC1=CC=C(F)C(F)=C1 AXNUZKSSQHTNPZ-UHFFFAOYSA-N 0.000 claims description 2
- OGIQUQKNJJTLSZ-UHFFFAOYSA-N 4-butylaniline Chemical compound CCCCC1=CC=C(N)C=C1 OGIQUQKNJJTLSZ-UHFFFAOYSA-N 0.000 claims description 2
- XTAZYLNFDRKIHJ-UHFFFAOYSA-N n,n-dioctyloctan-1-amine Chemical compound CCCCCCCCN(CCCCCCCC)CCCCCCCC XTAZYLNFDRKIHJ-UHFFFAOYSA-N 0.000 claims description 2
- QNIVIMYXGGFTAK-UHFFFAOYSA-N octodrine Chemical compound CC(C)CCCC(C)N QNIVIMYXGGFTAK-UHFFFAOYSA-N 0.000 claims description 2
- 230000005764 inhibitory process Effects 0.000 abstract description 13
- 238000005292 vacuum distillation Methods 0.000 abstract description 8
- 230000008901 benefit Effects 0.000 abstract description 5
- 239000003921 oil Substances 0.000 description 28
- 239000002184 metal Substances 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- -1 ammonium carboxylate salt Chemical class 0.000 description 11
- HNNQYHFROJDYHQ-UHFFFAOYSA-N 3-(4-ethylcyclohexyl)propanoic acid 3-(3-ethylcyclopentyl)propanoic acid Chemical compound CCC1CCC(CCC(O)=O)C1.CCC1CCC(CCC(O)=O)CC1 HNNQYHFROJDYHQ-UHFFFAOYSA-N 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 239000000126 substance Substances 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 6
- 229910052698 phosphorus Inorganic materials 0.000 description 6
- 239000011574 phosphorus Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 239000010779 crude oil Substances 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 3
- 208000012839 conversion disease Diseases 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 2
- 239000005642 Oleic acid Substances 0.000 description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000005536 corrosion prevention Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000005504 petroleum refining Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000009972 noncorrosive effect Effects 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
- C23F11/14—Nitrogen-containing compounds
- C23F11/141—Amines; Quaternary ammonium compounds
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
- C23F11/12—Oxygen-containing compounds
- C23F11/128—Esters of carboxylic acids
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
The invention belongs to the technical field of corrosion inhibitors, and particularly relates to a corrosion inhibitor for an oil refining device, and a preparation method and application thereof. Adding 40-70 wt% of ricinoleic acid and 30-60 wt% of organic amine into a reaction kettle, heating to 120-150 ℃ under normal pressure, reacting at constant temperature for 2-5 hours, adding 1-5 wt% of benzene into the reaction kettle, and continuing to keep the temperature constant until water generated in the reaction is completely removed; and (3) when the temperature of the reaction system is reduced to below 50 ℃, adding 20-30 wt% of glacial acetic acid into the reaction system, heating to 120-150 ℃, reacting at constant temperature for 2-5 h until no water is removed, then cooling to below 100 ℃, and uniformly mixing the reaction product and a diluent to obtain the corrosion inhibitor for the oil refining device. The corrosion inhibitor is suitable for oil refining devices such as atmospheric and vacuum distillation, hydrogenation and the like, and has the advantages of small using amount, high corrosion inhibition efficiency, strong universality and the like.
Description
Technical Field
The invention belongs to the technical field of corrosion inhibitors, and particularly relates to a corrosion inhibitor for an oil refining device, and a preparation method and application thereof.
Background
The petroleum refining process has a plurality of corrosion problems, equipment corrosion not only has potential safety problems, but also increases production and maintenance cost and reduces the benefit of a factory on the whole. In refineries, crude oil is the major cause of corrosion of metal equipment. Inorganic salts, S-or N-containing compounds, CO present in crude oil in small amounts2Impurities such as acid and water are corrosive substances; in the petroleum processing process, other non-corrosive impurities can be converted into corrosive media which have a corrosive effect on equipment due to reaction, and although the content of the impurities is low, the impurities have great potential threat to the safety of metal equipment in an oil refinery. In the process of petroleum refining, various additives and acid-base substances added can also form corrosive media, thereby promoting the corrosion of metal equipment. Therefore, corrosion protection measures must be taken to ensure long-term operation of the device. In the existing anticorrosion measures, except for material anticorrosion, the process anticorrosion is mainly carried out by adding assistants, and the assistants usually comprise a demulsifier, a neutralizer, a corrosion inhibitor and the like. Corrosion inhibitors are substances that can prevent or slow down the corrosion of metals under certain conditions. Compared with other protection methods, the corrosion inhibitor has the function of corrosion prevention without changing the corrosion environment; the type and the dosage of the corrosion inhibitor can be changed along with the change of corrosion conditions without increasing the investment of corrosion prevention equipment so as to achieve the optimal corrosion inhibition effectFruits and the like. At present, more than 90% of oil refineries in China adopt measures of filling different corrosion inhibitors to reduce the corrosion conditions of different parts in different devices.
The corrosion inhibitor has the characteristics of high selectivity, loss, pollution, toxicity and the like, and the protection capability on equipment is influenced by various factors, such as the chemical composition and properties of the corrosion inhibitor, the injection concentration and temperature, the environmental pH value, the system flow rate and the like. Common corrosion inhibitors can be classified into oxidation type film corrosion inhibitors, adsorption type film corrosion inhibitors, precipitation type film corrosion inhibitors, reaction conversion type film corrosion inhibitors, and the like. The oxidation type film corrosion inhibitor directly or indirectly oxidizes the protected metal to form a metal oxide film on the surface of the protected metal, and the oxidation type film corrosion inhibitor has good compactness and strong adhesion with the metal. When the oxide film reaches a certain thickness, the oxidation reaction is slowed down, so that excessive corrosion inhibitor does not cause scaling or iron scale formation. The adsorption type film corrosion inhibitor enables the corrosion inhibitor to be adsorbed on the metal surface through the physical adsorption effect or the chemical adsorption effect of polar groups on the molecules of the corrosion inhibitor, increases the activation energy of corrosion reaction, hinders the transfer of charges or substances related to corrosion, and reduces the corrosion speed. The precipitation type film corrosion inhibitor and ions in a corrosive medium act to form a sediment film which is insoluble in water or water, and the sediment film has a protection effect on metals. The deposit film is less dense and less adhesive than the passive film, and therefore less effective than the oxide film. And the precipitated membrane may cause a side effect of scaling as the reaction is increased. The reaction conversion type film corrosion inhibitor is a reaction conversion film formed by the corrosion inhibitor, a corrosion medium and a metal surface through an interface reaction or conversion action, and a metal device is protected.
The Chinese invention patent CN 107190264A discloses an oil-soluble composite corrosion inhibitor, which comprises the following components by weight: 20-40 wt% of ammonium carboxylate salt, wherein the ammonium carboxylate salt is a mixture consisting of two or more than two of ammonium carboxylate salts prepared by respectively mixing vegetable oleic acid, animal oleic acid and naphthenic acid with tertiary alkyl primary amine in any proportion; 5-20 wt% of sulfonic amine salt, wherein the sulfonic amine salt is a mixture of two or more than two of sulfonic amine salts prepared from heavy alkylbenzene sulfonic acid, nonylphenol sulfonic acid and petroleum sulfonic acid and tertiary alkyl primary amine respectively in any proportion; 15-40 wt% of organic amine; 20 to 40 wt% of an organic solvent. The product of the invention has the advantages of stable performance, good oil solubility, strong corrosion resistance, good film forming property and the like. But the product has higher price and poorer high-temperature resistance.
The Chinese patent CN 105220158B discloses a non-phosphorus high-temperature corrosion inhibitor and a preparation method thereof. The non-phosphorus high-temperature corrosion inhibitor comprises 5-60 wt% of thiazoline thioether compound, 1-50 wt% of organic polysulfide compound, 1-30 wt% of organic amine compound and 10-70 wt% of solvent, wherein the weight of the non-phosphorus high-temperature corrosion inhibitor is calculated by the total weight of the non-phosphorus high-temperature corrosion inhibitor. The non-phosphorus high-temperature corrosion inhibitor provided by the invention can be used in a high-temperature naphthenic acid corrosion environment of an oil refining device, can obviously inhibit corrosion of naphthenic acid corrosion media on metal equipment and pipelines, and meanwhile, the corrosion inhibitor does not contain phosphorus elements and does not produce harm to subsequent processing devices. However, this product is only suitable for inhibiting naphthenic acid-induced corrosion in crude oil on H produced in hydrogenation units2The corrosion effect caused by S and HCl is not good.
The existing corrosion inhibitor for oil refining generally has the problems of large dosage, poor corrosion inhibition efficiency, single corrosion inhibition mechanism, poor universality and the like. Therefore, the development of corrosion inhibitors with the characteristics of small dosage, high corrosion inhibition efficiency, strong universality and the like is a development trend in the future.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a corrosion inhibitor for an oil refining device. The corrosion inhibitor is suitable for oil refining devices such as atmospheric and vacuum distillation, hydrogenation and the like, and has the advantages of small dosage, high corrosion inhibition efficiency, strong universality and the like; the invention also provides a preparation method thereof.
The preparation method of the corrosion inhibitor for the oil refining device comprises the following steps:
(1) adding 40-70 wt% of ricinoleic acid and 30-60 wt% of organic amine into a reaction kettle, heating to 120-150 ℃ under normal pressure, reacting at constant temperature for 2-5 hours, adding 1-5 wt% of benzene into the reaction kettle, and continuing to keep the temperature constant until water generated in the reaction is completely removed;
(2) and (3) when the temperature of the reaction system is reduced to below 50 ℃, adding 20-30 wt% of glacial acetic acid into the reaction system, heating to 120-150 ℃, reacting at constant temperature for 2-5 h until no water is removed, then cooling to below 100 ℃, and uniformly mixing the reaction product and a diluent to obtain the corrosion inhibitor for the oil refining device.
The percentage of each substance in the step (1) and the step (2) is the percentage of the total of each substance.
Wherein:
the organic amine in the step (1) is one or more of distearyl amine, trioctyl amine, 1, 5-dimethylhexylamine, 1, 10-decanediamine, 2, 6-dimethylaniline, 3, 5-dimethylaniline, 2,4, 6-trimethylaniline, p-butylaniline, 2, 3-dichloroaniline, 2, 4-dichloroaniline, 2, 6-dichloroaniline, 3, 4-dichloroaniline, 2,4, 5-trichloroaniline, 2,4, 6-trichloroaniline, 2, 4-dibromoaniline, 2, 4-difluoroaniline, 3, 4-difluoroaniline, 2,3, 4-trifluoroaniline or 1-naphthylamine.
The constant-temperature reaction temperature in the step (1) is preferably 135-150 ℃, and the reaction time is preferably 2-3.5 h, and more preferably 3 h.
The constant-temperature reaction temperature in the step (2) is preferably 135-150 ℃, and the reaction time is preferably 3 hours.
And (3) the diluent in the step (2) is one or more of gasoline, diesel oil, first line oil, second line oil, third line oil or deasphalted oil.
The mass ratio of the reaction product in the step (2) to the diluent is 40: 60-80: 20.
the corrosion inhibitor for the oil refining device is prepared by the preparation method of claim 1.
The corrosion inhibitor is applied to an atmospheric and vacuum distillation unit and/or a hydrogenation unit.
Compared with the prior art, the invention has the following beneficial effects:
by designing the molecular structure of the corrosion inhibitor, the corrosion inhibitor molecule and the iron lattice site on the surface of the oil refining device have strong interaction energy, and effectively inhibit the active iron lattice site and the corrosive factors (such as naphthenic acid in crude oil and H generated by a hydrogenation device)2S, HCl and the like) to show high-efficiency corrosion inhibition effectAnd (4) rate. Therefore, the corrosion inhibitor for oil refining devices such as atmospheric and vacuum distillation, hydrogenation and the like provided by the invention has the characteristics of small dosage, high corrosion inhibition efficiency, strong universality and the like.
Detailed Description
The present invention is further described below with reference to examples.
Example 1
Adding 40 wt% of ricinoleic acid and 60 wt% of distearyl amine into a reaction kettle, heating to 135 ℃ by adopting steam, reacting for 3 hours at constant temperature, adding 3 wt% of benzene into the reaction kettle, keeping the constant temperature, and carrying and removing water generated in the reaction until the water generated in the reaction is completely removed; when the temperature of the reaction system is reduced to 50 ℃, adding 30 wt% of glacial acetic acid into the reaction system, heating to 140 ℃ by adopting steam, reacting for 2 hours at constant temperature, and reacting until no water is generated; and then cooling to below 100 ℃, and uniformly mixing the reaction product and the deasphalted oil according to the mass ratio of 70:30 to obtain the corrosion inhibitor for oil refining devices such as atmospheric and vacuum distillation, hydrogenation and the like.
Example 2
Adding 55 wt% of ricinoleic acid and 45 wt% of 2, 6-dichloroaniline into a reaction kettle, heating to 148 ℃ by adopting steam, reacting for 3.5 hours at constant temperature, adding 4 wt% of benzene into the reaction kettle, keeping the constant temperature, and carrying and removing water generated in the reaction until the water generated in the reaction is completely removed; when the temperature of the reaction system is reduced to 48 ℃, adding 20 wt% of glacial acetic acid into the reaction system, heating to 142 ℃ by adopting steam, reacting for 3 hours at constant temperature, and reacting until no water is generated; and then cooling to below 100 ℃, and uniformly mixing the reaction product and the gasoline according to the mass ratio of 45:55 to obtain the corrosion inhibitor for oil refining devices such as atmospheric and vacuum distillation, hydrogenation and the like.
Example 3
Adding 70 wt% of ricinoleic acid and 30 wt% of 1-naphthylamine into a reaction kettle, heating to 150 ℃ by adopting steam, reacting for 2.5 hours at constant temperature, then adding 2.5 wt% of benzene into the reaction kettle, keeping the constant temperature, and carrying and removing water generated in the reaction until the water generated in the reaction is completely removed; when the temperature of the reaction system is reduced to 45 ℃, adding 22 wt% of glacial acetic acid into the reaction system, heating the mixture to 145 ℃ by adopting steam, reacting for 2.5 hours at constant temperature, and reacting until no water is generated; and then cooling to below 100 ℃, and uniformly mixing the reaction product and the first-line oil according to the mass ratio of 55:45 to obtain the corrosion inhibitor for oil refining devices such as atmospheric and vacuum refining, hydrogenation and the like.
Example 4
Adding 60 wt% of ricinoleic acid and 40 wt% of 3, 5-dimethylaniline into a reaction kettle, heating to 137 ℃ by adopting steam, reacting for 3 hours at constant temperature, then adding 5 wt% of benzene into the reaction kettle, keeping the constant temperature, and carrying and removing water generated in the reaction until the water generated in the reaction is completely removed; when the temperature of the reaction system is reduced to 50 ℃, adding 26 wt% of glacial acetic acid into the reaction system, heating to 140 ℃ by adopting steam, reacting for 4 hours at constant temperature, and reacting until no water is generated; and then cooling to below 100 ℃, and uniformly mixing the reaction product and the third line oil according to the mass ratio of 80:20 to obtain the corrosion inhibitor for oil refining devices such as atmospheric and vacuum distillation, hydrogenation and the like.
Example 5
Adding 60 wt% of ricinoleic acid and 40 wt% of 1, 10-decamethylene diamine into a reaction kettle, heating to 145 ℃ by adopting steam, reacting for 3 hours at constant temperature, adding 4 wt% of benzene into the reaction kettle, keeping the constant temperature, and carrying and removing water generated in the reaction until the water generated in the reaction is completely removed; when the temperature of the reaction system is reduced to 45 ℃, adding 24 wt% of glacial acetic acid into the reaction system, heating the mixture to 145 ℃ by adopting steam, reacting for 5 hours at constant temperature, and reacting until no water is generated; and then cooling to below 100 ℃, and uniformly mixing the reaction product and diesel oil according to the mass ratio of 70:30 to obtain the corrosion inhibitor for oil refining devices such as atmospheric and vacuum distillation, hydrogenation and the like.
The naphthenic acid system is used for evaluating the corrosion inhibition effect of the corrosion inhibitor, and the specific method comprises the following steps: adding 800mL of industrial white oil (acid value is 20mg KOH/g) containing naphthenic acid medium into a 1L high-temperature high-pressure reaction kettle, adding the corrosion inhibitor of the embodiment 1-5 with a certain concentration, then immersing a pretreated and accurately weighed No. 20 carbon steel test piece into a test oil product by using a special hook, and carrying out a corrosion inhibitor performance evaluation test under the conditions of test temperature of 280-380 ℃, rotation speed of 800rpm and test period of 96 hours. After the test is finished, the test piece is cooled to room temperature, and then the test piece is taken out and processed according to the procedures of the standard ASTM G1-2003, and then the test piece is accurately weighed. The blank test was performed as above except that no corrosion inhibitor was added during the test. The test results are shown in Table 1.
TABLE 1 evaluation of the effectiveness of different corrosion inhibitors in naphthenic acid systems
The prepared corrosion medium is 1000mg/L HCl +1000mg/L NaCl +200mg/L H2S aqueous solution, adding a certain concentration of the corrosion inhibitors prepared in examples 1-5, and examining the corrosion inhibition performance of different corrosion inhibitors, the results are shown in Table 2.
TABLE 2 different corrosion inhibitors in HCl-H2Evaluation Effect in S System
As can be seen from the evaluation results in tables 1 and 2, the corrosion inhibitor provided by the invention can be used in naphthenic acid corrosion environment and HCl-H2In S corrosion environment, a small amount of the corrosion inhibitor is added to show higher corrosion inhibition rate, and the corrosion inhibition rate exceeds 96 percent. The results show that the corrosion inhibitor provided by the invention has the advantages of small dosage, high corrosion inhibition efficiency, strong universality and the like.
Claims (5)
1. A preparation method of a corrosion inhibitor for an oil refining device is characterized by comprising the following steps: the method specifically comprises the following steps:
(1) adding 55-70 wt% of ricinoleic acid and 30-45 wt% of organic amine into a reaction kettle, heating to 120-150 ℃ under normal pressure, reacting at constant temperature for 2-5 hours, adding 1-5 wt% of benzene into the reaction kettle, and continuing to keep the temperature constant until water generated in the reaction is completely removed;
(2) when the temperature of the reaction system is reduced to below 50 ℃, adding 20-26 wt% of glacial acetic acid into the reaction system, heating to 120-150 ℃, reacting at constant temperature for 2-5 hours until no water is removed, then cooling to below 100 ℃, and uniformly mixing a reaction product and a diluent to obtain the corrosion inhibitor for the oil refining device;
wherein: the diluent in the step (2) is one or more of gasoline, diesel oil, first line oil, second line oil, third line oil or deasphalted oil; the mass ratio of the reaction product in the step (2) to the diluent is 40: 60-80: 20;
the organic amine in the step (1) is one or more of distearyl amine, trioctyl amine, 1, 5-dimethylhexylamine, 1, 10-decanediamine, 2, 6-dimethylaniline, 3, 5-dimethylaniline, 2,4, 6-trimethylaniline, p-butylaniline, 2, 3-dichloroaniline, 2, 4-dichloroaniline, 2, 6-dichloroaniline, 3, 4-dichloroaniline, 2,4, 5-trichloroaniline, 2,4, 6-trichloroaniline, 2, 4-dibromoaniline, 2, 4-difluoroaniline, 3, 4-difluoroaniline, 2,3, 4-trifluoroaniline or 1-naphthylamine.
2. The method for producing a corrosion inhibitor for an oil refinery according to claim 1, wherein: the constant-temperature reaction temperature in the step (1) is 135-150 ℃, and the reaction time is 2-3.5 h.
3. The method for producing a corrosion inhibitor for an oil refinery according to claim 1, wherein: the constant-temperature reaction temperature in the step (2) is 135-150 ℃, and the reaction time is 3 hours.
4. A corrosion inhibitor for oil refining equipment is characterized in that: prepared by the preparation method of claim 1.
5. The application of the corrosion inhibitor for the oil refining device is characterized in that: the corrosion inhibitor prepared by the preparation method of claim 1 is applied to an atmospheric and vacuum device and/or a hydrogenation device.
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